Polyamide compositions and processes

ABSTRACT

A polyamide comprising a nylon and a polyetheramine. The polyetheramine can have a molecular weight of at least 1500 an Amine Hydrogen Equivalent Weight (AHEW) of less than 10 percent higher than the idealized AHEW for the polyetheramine. The polyamide may have a moisture regain ranging from about 10% to about 30%.

BACKGROUND OF THE INVENTION

Over the years there have been a number of approaches to incorporatepolyether segments in to polyamides with the objective of improving theproperties of yarns made from such polyamides. The desirable property ofhydrophilicity in nylon yarns for use in apparel applications is oftenimparted through incorporation of oxyethylene (—OCH₂CH₂—) repeat units.Substantial study has been undertaken to find the right balance ofoxyethylene repeat units in the polyamide polymer backbone. As a result,such a modified polymer may require altered polymerization conditionsand the yarn spinning conditions are not readily predictable or readilyadapted to conventional spinning assets.

In the 1980's, Allied introduced a hydrophilic nylon based upon 15 wt %Jeffamine® ED-2001 in Nylon 6 (polycaproamide) under the trade nameHydrofil® nylon. The polymer was made by heating caprolactam with 5%aminocaproic acid (to induce polymerization) and the Jeffamine® ED-2001at 255° C. After extrusion of the polymer into pellets, the polymercomposition is water extracted 5 times at 100° C. to remove residualcaprolactam and then dried for 16 hrs. Such extraction and drying aretypical disadvantages for any Nylon 6 based polymer over a Nylon 6,6based polymer.

In a known approach, using the PEBAX® range of thermoplastic elastomersfrom Arkema Inc, (King of Prussia, Pa., USA), polyetherglycols(polyethers with hydroxyl end groups) are reacted with diacids (e.g.,adipic acid) and nylon polymer monomers (e.g., nylon 66 “salt,”caprolactam, aminoacids). The resulting nylon polymer is apolyetheresteramide. These are block copolymers of the polyether and thepolyamide linked together with an ester group. Such polymers are madeusing high vacuum (<10 torr) polycondensation processes. The esterlinkages formed in such polymers are known to be susceptible tohydrolysis, and therefore, vacuum drying to very low moisture content isrequired.

Additionally, a treated textile article formed from a synthetic fibersubstrate including a polyamide treatment agent for improved moisturetransport is described in WO2003/044263. The polyamide treatment agentincludes a hydrophobic component and a hydrophilic component. In anembodiment described therein, the hydrophobic component is between about19% and 95% (mole percent) of the polyamide treatment agent. Inaddition, the polyamide treatment agent may include effective amounts ofany one of an oxyalkylene derivative, an ether linkage, and anoxyalkylene derivative and an ether linkage.

In another approach, the polyether used has amine end groups at each endof the polyether chain. When this polyetherdiamine is reacted with adiacid (e.g., adipic acid) and a nylon monomer (nylon 66 salt orcaprolactam) the resulting polymers are polyetheramides. Again, they areblock copolymers of polyether and polyamide but now linked with an amidebond. As there are no ester groups present, the polymerization may beless troublesome and does not normally employ high vacuum. However,incorporation of the polyether can be challenging, includinginconsistent polymer compositions, poor processing properties, etc. Forexample, such polyetheramides may not provide spinnable compositions forsubsequent processing into yarn.

As such, synthetic polyamide compositions continue to be researched anddeveloped.

SUMMARY OF THE INVENTION

The disclosures herein relate to synthetic polyamide compositions andmethods for the production thereof. Generally, the present polyamidecompositions include polyether segments and a nylon.

In particular, one aspect of the present invention is a polyamidewherein the polyamide comprises a nylon and a polyetherdiamine, thepolyetherdiamine having a molecular weight of at least 1500 and an AmineHydrogen Equivalent Weight (AHEW) of less than 10 percent higher thanthe idealized AHEW for the polyetherdiamine, and preferably wherein thepolyamide has a moisture regain ranging from about 10% to about 30%.

In another aspect the present invention relates to a process forproducing a polyamide which comprises contacting a diacid, apolyetherdiamine, and a nylon salt; forming a mixture; heating themixture in a closed vessel to a temperature and autogenous pressuresufficient to cause polymerization of the mixture; and forming apolyamide; preferably where the polyamide is characterized by a moistureregain of about 10% to about 30%.

In another aspect the present invention relates to a non-apparel textileyarn comprising a polyamide, said polyamide comprising a nylon and apolyetherdiamine, the polyetherdiamine having a molecular weight of atleast 1500 and an Amine Hydrogen Equivalent Weight (AHEW) of less than10 percent higher than the idealized AHEW for the polyetherdiamine, andpreferably wherein the polyamide has a moisture regain value rangingfrom about 10% to about 30%.

In one embodiment, the non-apparel textile yarn of the present inventionis a textile yarn which is suitable for and limited to making textilesor fabrics other than apparel textiles or apparel fabrics. In oneembodiment, the non-apparel textile yarn of the present invention isused only in making textiles or fabrics other than apparel textiles orfabrics.

In another aspect, the present invention relates to a non-appareltextile or fabric.

In another aspect, the present invention provides the use of the yarnsdisclosed herein for the purpose of producing a non-apparel textile orfabric.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a differential scanning calorimetry (DSC) plot of a polyamidein accordance with one embodiment of the present disclosure.

FIG. 2 is a differential scanning calorimetry (DSC) plot of a polyamidein accordance with one embodiment of the present disclosure.

FIG. 3 is a differential scanning calorimetry (DSC) plot of a polyamidein accordance with one embodiment of the present disclosure.

FIG. 4 is a differential scanning calorimetry (DSC) plot of a polyamidein accordance with one embodiment of the present disclosure.

FIG. 5 is a differential scanning calorimetry (DSC) plot of a polyamidein accordance with one embodiment of the present disclosure.

FIG. 6 is a differential scanning calorimetry (DSC) plot of a polyamidein accordance with one embodiment of the present disclosure.

FIG. 7 is a differential scanning calorimetry (DSC) plot of a polyamidein accordance with one embodiment of the present disclosure.

FIG. 8 is a plot showing moisture uptake of polyamides in accordancewith the present invention.

It should be noted that the figures are merely exemplary of severalembodiments of the present invention and no limitations on the scope ofthe present invention are intended thereby.

DETAILED DESCRIPTION OF THE INVENTION

Although the following detailed description contains many specifics forthe purpose of illustration, a person of ordinary skill in the art willappreciate that many variations and alterations to the following detailsare within the scope of the herein disclosed embodiments.

Accordingly, the following embodiments are set forth without any loss ofgenerality to, and without imposing limitations upon any claimedinvention. Before the present disclosure is described in greater detail,it is to be understood that this disclosure is not limited to particularembodiments described, as this may vary. It is also to be understoodthat the terminology used herein is for the purpose of describingparticular embodiments only, and is not intended to be limiting, sincethe scope of the present disclosure will be limited only by the appendedclaims. Unless defined otherwise, all technical and scientific termsused herein have the same meaning as commonly understood by one ofordinary skill in the art to which this disclosure belongs.

As used in this specification and the appended claims, the singularforms “a,” “an” and “the” include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “apolyamide” includes a plurality of polyamides.

In this disclosure, “comprises,” “comprising,” “containing” and “having”and the like can have the meaning ascribed to them in U.S. Patent lawand can mean “includes,” “including,” and the like, and are generallyinterpreted to be open ended terms. The term “consisting of” is a closedterm, and includes only the components, structures, steps, or the likespecifically listed, and that which is in accordance with U.S. Patentlaw. “Consisting essentially of” or “consists essentially” or the like,when applied to methods and compositions encompassed by the presentdisclosure refers to compositions like those disclosed herein, but whichmay contain additional structural groups, composition components ormethod steps. Such additional structural groups, composition componentsor method steps, etc., however, do not materially affect the basic andnovel characteristic(s) of the compositions or methods, compared tothose of the corresponding compositions or methods disclosed herein. Infurther detail, “consisting essentially of” or “consists essentially” orthe like, when applied to methods and compositions encompassed by thepresent disclosure have the meaning ascribed in U.S. Patent law and theterm is open-ended, allowing for the presence of more than that which isrecited (e.g., trace contaminants, components not reactive with thepolymer or components reacted to form the polymer, and the like) so longas basic or novel characteristics of that which is recited is notchanged by the presence of more than that which is recited, but excludesprior art embodiments. When using an open ended term, like “comprising”or “including,” it is understood that direct support should be affordedalso to “consisting essentially of” language as well as “consisting of”language as if stated explicitly.

The term Amine Hydrogen Equivalent Weight (AHEW) is defined as themolecular weight of the polyetheramine divided by the number of activeamine hydrogen per molecule. For illustration, an idealizedpolyetherdiamine having an average molecular weight of 2000 and whereall the ends of the polyether were amine ends, hence contributing 4.0active amine hydrogens per molecule, would have an AHEW of 500 g perequivalent. If, for comparison, 10 percent of the ends were in facthydroxyl rather than amine, then there would be only 3.6 active aminehydrogens per molecule and the polyetheramine would have an AHEW of 556g per equivalent. The number of active amine hydrogen per molecule, andtherefore the AHEW, of a given polyetheramine can be calculatedaccording to known and conventional techniques in the art, however it ispreferably calculated by determining the amine group nitrogen contentusing the procedure described in ISO 9702.

The term “aliphatic group” refers to a saturated or unsaturated linearor branched hydrocarbon group and encompasses alkyl, alkenyl, andalkynyl groups, for example.

The terms “alk” or “alkyl” refer to straight or branched chainhydrocarbon groups having 1 to 12 carbon atoms, for example 1 to 8carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl,i-butyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, dodecyl, octadecyl,amyl, 2-ethylhexyl, and the like. An alkyl group is optionallysubstituted, unless stated otherwise, with one or more groups, selectedfrom aryl (optionally substituted), heterocyclo (optionallysubstituted), carbocyclo (optionally substituted), halo, hydroxy,protected hydroxy, alkoxy (e.g., C1 to C7) (optionally substituted),acyl (e.g., C1 to C7), aryloxy (e.g., C1 to C7) (optionallysubstituted), alkylester (optionally substituted), arylester (optionallysubstituted), alkanoyl (optionally substituted), aroyl (optionallysubstituted), carboxy, protected carboxy, cyano, nitro, amino,substituted amino, (monosubstituted)amino, (disubstituted)amino,protected amino, amido, lactam, urea, urethane, sulfonyl, and the like.

The term “alkenyl” refers to straight or branched chain hydrocarbongroups having 2 to 12 carbon atoms, for example 2 to 4 carbon atoms, andat least one double carbon to carbon bond (either cis or trans), such asethenyl. An alkenyl group is optionally substituted, unless statedotherwise, with one or more groups, selected from aryl (includingsubstituted aryl), heterocyclo (including substituted heterocyclo),carbocyclo (including substituted carbocyclo), halo, hydroxy, alkoxy(optionally substituted), aryloxy (optionally substituted), alkylester(optionally substituted), arylester (optionally substituted), alkanoyl(optionally substituted), aroyl (optionally substituted), cyano, nitro,amino, substituted amino, amido, lactam, urea, urethane, sulfonyl, andthe like.

The term “alkynyl” refers to straight or branched chain hydrocarbongroups having 2 to 12 carbon atoms, for example 2 to 4 carbon atoms, andat least one triple carbon to carbon bond, such as ethynyl. An alkynylgroup is optionally substituted, unless stated otherwise, with one ormore groups, selected from aryl (including substituted aryl),heterocyclo (including substituted heterocyclo), carbocyclo (includingsubstituted carbocyclo), halo, hydroxy, alkoxy (optionally substituted),aryloxy (optionally substituted), alkylester (optionally substituted),arylester (optionally substituted), alkanoyl (optionally substituted),aroyl (optionally substituted), cyano, nitro, amino, substituted amino,amido, lactam, urea, urethane, sulfonyl, and the like.

Phrases such as “suitable to provide,” “sufficient to cause,” or“sufficient to yield,” or the like, in the context of methods ofsynthesis, refers to reaction conditions related to time, temperature,solvent, reactant concentrations, and the like, that are within ordinaryskill for an experimenter to vary to provide a useful quantity or yieldof a reaction product. It is not necessary that the desired reactionproduct be the only reaction product or that the starting materials beentirely consumed, provided the desired reaction product can be isolatedor otherwise further used.

It should be noted that ratios, concentrations, amounts, and othernumerical data may be expressed herein in a range format. It is to beunderstood that such a range format is used for convenience and brevity,and thus, should be interpreted in a flexible manner to include not onlythe numerical values explicitly recited as the limits of the range, butalso to include all the individual numerical values or sub-rangesencompassed within that range as if each numerical value and sub-rangeincludes “about ‘x’ to about ‘y’”. To illustrate, a concentration rangeof “about 0.1% to about 5%” should be interpreted to include not onlythe explicitly recited concentration of about 0.1 wt % to about 5 wt %,but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%)and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within theindicated range. In an embodiment, the term “about” can includetraditional rounding according to significant figures of the numericalvalue. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ toabout ‘y’”.

The term “about” as used herein, when referring to a numerical value orrange, allows for a degree of variability in the value or range, forexample, within 10%, or, in one aspect within 5%, of a stated value orof a stated limit of a range.

In addition, where features or aspects of the disclosure are describedin terms of a list or a Markush group, those skilled in the art willrecognize that the disclosure is also thereby described in terms of anyindividual member or subgroup of members of the Markush group. Forexample, if X is described as selected from the group consisting ofbromine, chlorine, and iodine, claims for X being bromine and claims forX being bromine and chlorine are fully described as if listedindividually. For example, where features or aspects of the disclosureare described in terms of such lists, those skilled in the art willrecognize that the disclosure is also thereby described in terms of anycombination of individual members or subgroups of members of list orMarkush group. Thus, if X is described as selected from the groupconsisting of bromine, chlorine, and iodine, and Y is described asselected from the group consisting of methyl, ethyl, and propyl, claimsfor X being bromine and Y being methyl are fully described andsupported.

As used herein, all percent compositions are given asweight-percentages, unless otherwise stated. When solutions ofcomponents are referred to, percentages refer to weight-percentages ofthe composition including solvent (e.g., water) unless otherwiseindicated.

As used herein, all molecular weights (Mw) of polymers areweight-average molecular weights, unless otherwise specified.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publication or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present disclosure is not entitled to antedate suchpublication by virtue of prior disclosure. Further, the dates ofpublication provided could be different from the actual publicationdates that may need to be independently confirmed.

As will be apparent to those of skill in the art upon reading thisdisclosure, each of the individual embodiments described and illustratedherein has discrete components and features that may be readilyseparated from or combined with the features of any of the other severalembodiments without departing from the scope or spirit of the presentdisclosure. Any recited method can be carried out in the order of eventsrecited or in any other order that is logically possible.

Embodiments of the present disclosure employ, unless otherwiseindicated, techniques of chemistry, and the like, which are within theskill of the art. Such techniques are explained fully in the literature.

The polyamides of the present invention are well-suited for makinghydrophilic polyamide compositions. As such, the disclosure hereingenerally also relates to improved synthetic polyamide (nylon) polymercompositions. Generally, the polyamides of the present inventioncomprise a nylon and a polyetheramine. As used herein, the term“composition” refers to a composition which is not a yarn or fibre or isnot a textile or fabric or garment containing such a yarn or fibre. Sucha composition is, however, suitable for making a yarn or fibre and atextile or fabric or garment containing such yarns or fibres.

Generally, such polyamides comprise a nylon and a polyetheramine and canhave a moisture regain ranging (measured as described herein) rangingfrom about 10% to about 30%, preferably from about 10 to about 25%,preferably from about 15 to about 25%. Such regain can allow forimproved processability during subsequent processing of the presentpolyamide compositions. For example, the polyamide can have anelongation to break of from 20% to 90% when spun into a yarn. Thepolyamide composition may be either an acid (anionic) or base (cationic)dyeable polymer, as discussed herein. In one embodiment, at least 85 percent of the polymer backbone (between amide units) can comprisealiphatic groups. The nylon discussed herein can be polyhexamethyleneadipamide (nylon 6,6), polycaproamide (nylon 6), or copolymers of eitherof these. In one embodiment, the nylon can be nylon 6,6. Generally, thenylon can be present in the polyamide in an amount ranging from about50% to 95% by weight.

The polyetheramine can be made by reacting polyethyleneglycol ofmolecular weight of about 2000 with three to four molecules ofpropyleneoxide to convert the primary terminal hydroxyl groups tosecondary hydroxyl ends. The secondary hydroxyl ends are subsequentlyconverted into amine groups. Incomplete conversion results in apolyetheramine product containing residual hydroxyl end groups, suchhydroxyl groups are incapable of forming amide groups during a polyamidepolymerization process, limiting the rate and degree of polymerization,and are hence undesirable. Such incomplete conversion is reflected inthe AHEW value of the polyetheramine being higher than the idealisedvalue. The Technical Data Sheet for Elastamine® RE-2000 describes thepolyetheramine as being a polyetherdiamine of approximate molecularweight 2000, hence it has an idealised AHEW of 500 g per equivalent, thedatasheet further reports the actual AHEW as being 505 g per equivalent.For comparison, the Technical Data Sheet for Jeffamine ED-2003 describesthe polyetheramine as being a polyetherdiamine of approximate molecularweight 2000; hence it also has an idealised AHEW of 500 g perequivalent, the datasheet further reports the actual AHEW as being 575 gper equivalent.

The polyamides generally comprise a polyetheramine with an AHEW lessthan 10 percent higher than the idealized AHEW for the polyetheramine.The polyetheramine is preferably a polyetherdiamine. In one embodiment,the polyetheramine can be an alkylpolyetheramine. In one aspect, thepolyetheramine can include aliphatic groups. In still another aspect,the polyetheramine can be Elastamine® RE-2000 (Huntsman InternationalLLC). In one embodiment, the polyetheramine can have the followingstructure:

In a further embodiment, the polyetheramine can be α,ω-diaminopoly(oxyalkylene-co-oxyalkylene ether) copolymer. In one aspect, theα,ω-diamino poly(oxyalkylene-co-oxyalkylene ether) copolymer can beα,ω-diamino poly(oxyethylene-co-oxytetramethylene ether) copolymer, asdisclosed in United States Patent Application No. 20120065362A1. Such apolyetheramine can be made by reacting polyethyleneglycol of molecularweight of about 2000 with three to four molecules of propyleneoxide toconvert the primary terminal hydroxyl groups to secondary hydroxyl ends.

As discussed herein, a polyetherdiamine can be employed in thepolymerization of nylon monomers to form a polyamide which may be spuninto nylon yarns which exhibit good hydrophilicity properties. Suchproperties can impart tactile aesthetics and wear comfort highly desiredin apparel goods manufactured from these yarns.

Furthermore, the polyetheramines can be present in the polyamide and canhave various molecular weights depending upon the desired properties ofthe resulting polymer, including processability as discussed herein. Inone embodiment, the polyetheramine can have a molecular weight of atleast 1500. In other aspects, the polyetheramine can have a molecularweight of at least 2500, or even at least 5000. Additionally, thepolyetheramine can be present in an amount ranging from about 1 wt % toabout 20 wt % of the polyamide. In one aspect, the polyetheramine can bepresent in an amount ranging from about 5 wt % to about 15 wt %,preferably from about 10 wt % to about 15 wt %. In another preferredembodiment, the polyetheramine is present in an amount from about 8 wt %to about 18 wt %.

The polyamides described herein can further comprise a diacid. In oneexample, the diacid can be aliphatic diacids containing from 6 to 12carbon atoms, terephthalic acid, isophthalic acid, and mixtures thereof.In one aspect, the diacid can be adipic acid. The diacid can be presentin the polymer in an amount to give substantially equimolar proportionsof acid groups to amine groups of the polyetheramine. The polyamidesdescribed herein can have various physical properties. In oneembodiment, the polyamide can have 42 to 49 amine end groupgram-equivalents per 1000 kilograms of polymer. Additionally, thepolyamide can have a relative viscosity ranging from about 35 to about45. In another embodiment, the relative viscosity can be calculatedbased on a formic acid test method according to ASTM D789-86 known atthe time of filing the present disclosure in the United States Patentand Trademark Office. The polyamide can have a yellowness index fromabout 30 to about 45. In a more detailed aspect, the polyamide can havean L* color coordinate from about 75 to about 85. In another aspect, thepolyamide can have an a* color coordinate from about −5 to about 5. Instill another aspect, the polyamide can have a b* color coordinate fromabout 5 to about 25.

Whiteness can be determined using a test method conforming to the CIEwhiteness rating for each sample. Samples can be measured individuallyfor whiteness (W) and yellowness (Y), using a GRETAG MACBETH “COLOR EYE”reflectance spectrophotometer. First, by determining the CIELAB colorcoordinates L, a* and b*; and then, calculating W and Y by means know inthe art (see: ASTM Method E313-1996 Standard Practice for CalculatingWhiteness and Yellowness Indices from Instrumentally Measured ColorCoordinates). Details of this measurement are found in Color Technologyin the Textile Industry 2nd Edition, published by Committee RA 36, AATCC(1997); see in this volume: Special Scales for White Colors by Haroldand Hunter, pp 140-146, and the references therein, all are incorporatedherein by reference in their entirety.

Additionally, the present polyamides can further comprise a catalyst. Inone embodiment, the catalyst can be present in the polyamide in anamount ranging from 10 ppm to 1,000 ppm by weight. In another aspect,the catalyst can be present in an amount ranging from 10 ppm to 100 ppmby weight. The catalyst can include, without limitation, phosphoricacid, phosphorous acid, hypophosphoric acid arylphosphonic acids,arylphosphinic acids, salts thereof, and mixtures thereof. In oneembodiment, the catalyst can be sodium hypophosphite, manganesehypophosphite sodium phenylphosphinate, sodium phenylphosphonate,potassium phenylphosphinate, potassium phenylphosphonate,hexamethylenediammonium bis-phenylphosphinate, potassiumtolylphosphinate, or mixtures thereof. In one aspect, the catalyst canbe sodium hypophosphite.

The polyamides and polyamide compositions in accordance with the presentinvention may include an “optical brightener.” Such an opticalbrightener can be provided according to the disclosures of United StatesPatent Application No. 20080090945 A1; POLYAMIDE COMPOSITION WITHIMPROVED HEAT STABILITY AND WHITENESS; to INVISTA NORTH AMERICA S.à r.l.

The polyamides and polyamide compositions in accordance with embodimentsdisclosed herein can be improved in whiteness appearance through theaddition of an optical brightener. Such polyamides can exhibit apermanent whiteness improvement and can retain this whitenessimprovement through operations such as heat setting. In one embodiment,the optical brightener can be present in the polyamide in an amountranging from 0.01 wt % to 1 wt %.

In another embodiment an improvement in whiteness appearance can beachieved by addition of a delustering agent, the delustering agent canbe titanium dioxide.

In addition, these polyamide compositions may contain an antioxidantstabilizer or an antimicrobial additive. Additionally, the polyamidecompositions may contain an anti-foaming additive. In one embodiment,the anti-foaming additive can be present in the polyamide in an amountranging from 1 ppm to 500 ppm by weight.

The polyamides of the present invention are inherently acid (anionic)dyeable, but may also be rendered into a basic (cationic) dyeing form bymodifying these polymers or copolymers with a cationic dye receptivemonomer copolymerized in the polymer. This modification makescompositions particularly receptive to coloration with base (cationic)dyes. 5-sodium sulfoisophthalic acid is an example of such a cationicdye receptive monomer.

In a further aspect, the present invention provides a process forproducing a polyamide, comprising contacting a diacid, apolyetherdiamine, and a nylon salt; forming a mixture; heating themixture in a closed vessel to a temperature and autogenous pressuresufficient to cause polymerization of the mixture; and forming thepolyamide.

The processes for producing the polyamides can further compriseproviding to the mixture a catalyst, including those discussed herein.The processes can further comprise providing an anti-foaming additive tothe mixture. The processes can further comprise providing an opticalbrightener to the mixture.

Generally, the nylon monomers of the polyamide can be added as a salt,aminoacid, or lactam. The nylon monomer can be a nylon 6,6 salt and canbe present in the polyamide in an amount ranging from about 50 wt % to95 wt %.

Various processing parameters can be used in the polymerization of thepresent polyamides including temperature and pressure. The temperaturecan range from about 190° C. to about 290° C. and the autogenouspressure can range from about 250 pounds per square inch absolute (psia)to about 300 pounds per square inch absolute (psia). Additionally, theheating can be performed under partial vacuum. The partial vacuumattained is subject to autoclave design and economic considerations withthe process.

Generally, the present polymerization can involve various serial heatingcycles. Such cycles can individually comprise a heating temperatureprofile and a pressure profile. Generally the intent is to keep thesystem fluid through a combination of temperature for sufficient melt,and water content for sufficient solubility. The serial heating cyclescan comprise: a first heating cycle (C1) having a temperature startingbetween 170 to 215° C. and finishing between 190 to 230° C. over aperiod of 20 to 40 minutes under a pressure of between 130 to 300 psia;a second heating cycle (C2) having a temperature starting between 190 to230° C. and finishing at between 240 to 260° C. over a period of 20 to45 minutes under a pressure of between 130 to 300 psia; a third heatingcycle (C3) having a temperature starting between 240 and 260° C. andfinishing between 250 to 320° C. over a period of between 15 to 45minutes under a pressure of between 300 psia to atmospheric pressure;and a fourth heating cycle (C4) having a temperature starting between250 to 320° C. and finishing between 250 to 320° C. over a period of 15to 80 minutes under a pressure of between atmospheric pressure and about200 mBar absolute vacuum. Finally the polymer is extruded using methodswell known in the art. Generally, the polyamide composition isinherently acid dyeable and may, as an option, comprise a cationicdyeable polymer. The polyamide composition can contain polyhexamethyleneadipamide (nylon 6,6), or polycaproamide (nylon 6), or copolymers ofeither of these.

Generally, the process for producing the polyamide composition may bemade by an autoclave process. The process may start with a concentratedslurry (the term slurry also incorporating the concept of a solution)prepared from an aqueous solution of a nylon salt, aminoacid or lactamor mixtures of e.g., a nylon 6,6 salt, that is provided to an autoclavevessel. Optionally, the slurry may be dilute and become moreconcentrated by means of an evaporation step. The slurry may be preparedfrom an aqueous solution of the monomers, such as, hexamethylene diamineand adipic acid, in the manner known in the art. In another specificembodiment, the slurry may contain a minor amount of nylon 6 monomerwith the aqueous solution of the nylon 6,6 monomers in the form of anaqueous caprolactam solution. The optionally added aqueous caprolactamsolution may be mixed with the nylon salt in an amount to provide anylon 6 content of about 0.5 wt % to about 10 wt %. In another specificembodiment the slurry may contain the polyetheramine along with aquantity of diacid to give substantially equimolar proportions of acidgroups to amine groups of the polyetheramine. The autoclave vessel maythen be heated to about 230° C. (or some other functional temperature)allowing the internal (autogenous) pressure to rise. A delusterant,titanium dioxide (TiO₂) may optionally be injected into the autoclaveand monomer mixture as an aqueous dispersion.

In one embodiment, an aqueous dispersion of a polyetheramine may beinjected to the mixture in the autoclave vessel along with a quantity ofa diacid, e.g., adipic acid, to give substantially equimolar proportionsof acid groups to amine groups of the polyetheramine The mixture maythen be heated in the autoclave to about 245° C. (or some otherfunctional temperature). While at this temperature, the autoclavepressure may be reduced to atmospheric pressure and further reduced inpressure by application of a vacuum in the known manner, to form thepolyamide composition. The autoclave, containing the polyamidecomposition, would be maintained at this temperature for about 30minutes. This step may be followed by further heating of the polyamidepolymer composition in the autoclave to about 285° C., for example, andintroducing dry nitrogen to the autoclave vessel and pressurizing theautoclave by introducing dry nitrogen to about 4 to about 5 bar absolutepressure. The polymer composition may be released from the autoclave byopening a port in the autoclave vessel and allowing the molten polyamidecomposition to flow from the vessel in the form of laces. These lacesmay be cooled and quenched the in a current of water. Next, the laces ofpolyamide polymer may be granulated by known means and further cooledwith water.

The autoclave process described above can provide a polyamidecomposition with a formic acid method RV of about 25 to about 60. Inanother embodiment, the autoclave process described above can provide apolyamide composition with a formic acid method RV of about 38 to about45.

Optionally, the process may be modified to make a polyamide compositionhaving about 25 to about 130 gram equivalents of amine ends per 1000kilograms of polymer, provided by the addition of an excess of anaqueous hexamethylene diamine solution to the aqueous solution of nylonsalt.

The nylon polymers and copolyamides described herein can be inherentlyacid-dyeable. In one embodiment, the number of free amine end groups(AEG) in these polymers is at least 25 gram equivalents per 1000kilograms of nylon polymer. In order to make the polymers more deeplyacid dyeing, an enhanced level of free amine end groups can be utilized.More deeply acid dyeing nylon polymers have an enhanced AEG level, e.g.,at least 35 gram equivalents per 1000 kilograms of nylon polymer or AEGlevels of 60 to 130 gram equivalents per 1000 kilograms of nylon polymermay be used.

Furthermore, it is noted that a masterbatch of polyetheramine comprisingthe amine end equivalent of a suitable diacid, e.g. adipic acid, can bemade. This masterbatch can then be provided to the autoclave process. Inan alternative embodiment, the polyamide composition herein may be madeby a masterbatch process in which a flake or melt form is usedcomprising a polyetheramine dispersed in nylon, either nylon 6,6 ornylon 6. The flake or melt form is then subsequently added as amasterbatch comprising the nylon. In an embodiment, the masterbatchnylon flake containing the polyetheramine and the nylon, in flake form,are both melted. In an embodiment, the nylon flake containingpolyetheramine is melted and added to the nylon melt. In either case,the melt is forced from an extruder to a pump, which pumps the polyamidecompositions to a pack and a spinneret for making yarns, for example.

The nylon polymers and copolyamides described herein may also berendered into a basic dyeing form, i.e., receptive to coloration withbase dyes also called cationic dyes. Such base-dyeing compositions aremade from polyamide polymer with a cationic dye modifier copolymerizedin the polymer. U.S. Pat. No. 5,164,261 to Windley describes thepreparation of such cationic dye modified polyamides. In one embodiment,the polymer can be modified during polymerization with from 0.5 wt % to4 wt % of a cationic dye modifier, e.g., 5-sulfoisophthalic acid.Typically, a weighed quantity of the sodium salt of 5-sulfoisophthalicacid can be combined with a known amount of the polyamide precursor saltin an autoclave using standard polymerization procedures known in theart. In one embodiment, the amount of cationic dye modifier present inthe polymer can be from about 0.75 wt % to about 3 wt %, as determinedby total sulfur analysis of the polymer. This amount of cationic dyemodifier is reported as equivalent sulfonate groups. The sulfonate groupconcentration can be at least 25 gram equivalents per 1000 kilogramspolymer up to about 150 gram equivalents per 1000 kilograms polymer.

The polyamide composition of the present disclosure is particularlyuseful when spun into yarns. In one embodiment, the polyetheramine canbe provided to the polyamide composition, and hence inherent to the yarnitself when formed into a fabric, as opposed to being applied on afabric. In one embodiment, said yarn exhibits improved hydrophilicproperties as measured by various water wicking and moisture regaintests.

A yarn made from the polyamides described hereincan be a multifilamenttextile yarn in the form of either a low orientation yarn (LOY), apartially oriented yarn (POY) or a fully drawn yarn (FDY). The yarn maybe a textured yarn made from partially oriented yarn. Moreover, the yarnmay be substantially continuous, i.e. formed by one or more continuousfilaments. In other embodiments, a continuous filament can be cut intostaple fibers and the latter can be converted into a continuous threadby a spinning process, resulting in a continuous article of manufactureor comprised of shorter fibers. Such yarns may be used to make fabrics,which in turn may be used to make garments.

In one embodiment, apparatuses and methods for spinning yarns aredisclosed in U.S. Pat. No. 6,855,425, and similar techniques can belikewise in the context of the polyamides prepared and described herein.

Yarns made from the polyamides described hereinmay be textile yarns thatare especially useful for apparel fabric applications. That is to say,yarns having a yarn weight of from 5 to 300 dtex, and a filament weightof from 0.5 to 7 dtex can be desirable. In certain embodiments, the yarncomprises from 1 to 300 filaments. According to some embodiments theyarn comprises 3 to 150 filaments.

According to some embodiments the yarn has a DPF (dtex per filament)from 0.5 to 2.5, for example from 1 to 1.5.

Yarns made from the polyamides described herein can have a filamentuniformity in Uster percent (U %) of 1.5% or less, more typically 1% orless. Such uniformity can be desirable in order for the yarn to have thehigh appearance uniformity needed for apparel applications, and also toreduce yarn breaks in texturing, weaving and knitting operations.

Yarns made from the polyamides described herein can have an elongationto break of from 20% to 120%. According to some embodiments the yarnshave an elongation to break of from 20% to 90%. Typically, the yarnshave a tenacity of from 25 to 65 cN/tex, for example from 30 to 45cN/tex. These tensile properties are all desirable for apparel textileapplications.

In certain embodiments, the yarn of the polyamide can have a titaniumdioxide content less than 0.1 wt %, and more typically, less than 0.01wt %, giving the yarn a clear or bright luster. In other embodiments,the yarn of the polyamide can have a titanium dioxide content greaterthan 0.3 wt % and or even greater than 2 wt %, giving the yarn a matt ordull luster. Titanium dioxide content between these ranges can also beused, e.g., from 0.1 wt % to 0.3 wt %, as well.

In one specific embodiment, yarns of the polyamide may be prepared byusing known melt spinning process technology. With such technology, thegranulated polyamide composition made by using the autoclave process, orthe melt made by the masterbatch process, can both have an opticalbrightener therein as described above, and can be provided to thespinning machine. The molten polymer is forwarded by a metering pump toa filter pack, and extruded through a spinneret plate containingcapillary orifices of a shape chosen to yield the desired filamentcross-section at the spinning temperature. These cross-sectional shapesknown in the art can include circular, non-circular, trilobal, hollowand diabolo shapes. Typical hollow filaments can be produced asdisclosed in U.S. Pat. No. 6,855,425. Spinning temperatures can rangefrom 270° C. to 300° C., for example. The bundle of filaments emergingfrom the spinneret plate is cooled by conditioned quench air, treatedwith spin finish (an oil/water emulsion), optionally interlaced, e.g.using an interlacing air jet.

In some embodiments the continuous yarn thus obtained is cut andtransformed into staple fibers, which are subsequently used to producethreads or yarns by spinning, or for manufacturing nonwovens, byhydro-entanglement, needlepunching, ultrasonic bonding, chemicalbonding, heat bonding or the like.

In the case of FDY, the in-line processing on the spinning machinetypically includes making several turns around a set of Godet rolls(feed rolls), the number of turns being sufficient to prevent slippageover these rolls, then passing the yarn over another set of rolls (drawrolls) rotating at sufficient speed to stretch the yarn by apredetermined amount (the draw ratio). Finally, the process is continuedby heat setting and relaxing the yarn with a steam-box before winding upat a speed of at least 3000 m/min, preferably at least 4000 m/min, forexample 4800 m/min or more. Optionally, an alternative heat setting (orrelaxing) method can be used, such as heated rolls, and an additionalset of Godet rolls may be incorporated between draw rolls and winder tocontrol the tension while the yarn is set or relaxed. Also, optionally,a second application of spin finish and/or additional interlacing may beapplied before the final winding step.

In the case of POY, the additional in-line processing typically includesonly making an S-wrap over two Godet rolls rotating at the same speed,and then passing the yarn to a high speed winder, winding at a speed ofat least 3000 m/min, preferably at least 4000 m/min, for example 4800m/min or more. Use of the S-wrap is beneficial to control tension, butnot essential. Such a POY may be used directly as a flat yarn forweaving or knitting, or as a feedstock for texturing.

The LOY spinning process is similar to POY except that a windup speed of1000 m/min or below is used. These low orientation yarns, in general,are further processed via a second stage, e.g., on a conventionaldraw-twister or draw-wind machine.

In one embodiment, the polyamide polymer disclosed herein can be highlysuited for spinning into continuous filaments which may be converged toform multifilament yarns. The process of spinning synthetic polymers ascontinuous filaments and forming multifilament yarns is known to theskilled person. In general, successful spinning of filaments uses aspinneret plate having at least a single capillary orifice. Thecapillary orifices correspond to each individual filament comprising theyarn. Circular and non-circular cross-section spinneret capillaryorifices (or extrusion orifice) are employed depending upon the crosssectional shape sought for the filament. In general, for a certainpolymer throughput G (e.g., in grams per minute) per capillary, thefollowing equation applies:

G=ρ _((melt)) D ² _((capillary))(π/4)v _((extrusion))  Equation 1.

In this equation, ρ is the polymer melt density (e.g., for melted nylon6,6 at 290° C. equal to 1.0 gram per cm³), D is the diameter (equal totwice the radius) of the capillary assuming a circular orifice, and v isthe velocity of the filament. The extrusion velocity is given by thefollowing equation:

v _((extrusion)) =G(4/π)D ² _((capilliary))ρ_((melt))  Equation 2.

In one embodiment, the polymer is extruded at an extrusion velocity inthe range of 20 centimeters per second to 80 centimeters per second. Inanother embodiment, the freshly extruded filaments can be quenched withconditioned air in the known manner. In this step, the individualfilaments are cooled in a quench cabinet with a side draft ofconditioned air and converged and oiled with a primary finish, as knownin the art, into a yarn. The yarn is forwarded by feed roll onto a drawroll pair where the yarn is stretched and oriented to form a drawn yarnwhich is directed by roll into a yarn stabilization apparatus. Such astabilization apparatus is common to the art and here optionallyemployed as a yarn post-treatment step. Finally, the yarn is wound up asa yarn package at a yarn speed in the range of 1000 to 6500 meters perminute. The yarn RV (or relative viscosity by the formic acid method) isabout 51 to about 54.

In an embodiment, the yarn is a drawn yarn with elongation of 22% toabout 60%, the boiling water shrinkage is in the range of 3% to about10%, the yarn tenacity is the range of 3 to about 7 grams per denier,and the RV of the yarn can be varied and controlled well within a rangeof about 40 to about 60. The yarn is a dull luster multifilamentpolyamide yarn.

A derived parameter characterizing the superior properties of this yarnis called the Yarn Quality and found by the product of the yarn tenacity(grams per denier) and the square root of the % elongation, as inEquation 3.

YARN QUALITY=tenacity×(elongation)^(1/2)  Equation 3.

The Yarn Quality is an approximation to the measure of yarn “toughness.”As is known to those skilled in the art, the area under the yarn loadelongation curve is proportional to the work done to elongate the yarn.Where tenacity is expressed in terms of force per unit denier, forexample, and the elongation expressed as a per cent change per unit oflength, the load elongation curve is the stress-strain curve. In thiscase the area under the stress-strain curve is the work to extend theyarn or the yarn toughness. The yarn quality improvement provides anapparel polyamide yarn which is more acceptable in varied applications.These applications may include, without limitation, warp knit fabrics,circular knit fabrics, seamless knit garments, hosiery products,nonwoven fabrics and light denier technical fabrics.

In certain embodiments, the polyamide yarns have different dyeingcharacteristics with anionic dyes or cationic dyes. These dyeingcharacteristics may arise from different numbers of amine end groups.The concentration of amine end groups (AEG) influences how deeply thepolyamide is dyed by anionic dyes. Alternatively or additionally, thepolyamides may contain anionic end groups, such as sulfonate orcarboxylate end groups, that render the polyamide cationic-dyeable.

In certain embodiments, the polyamide yarns are dyed with fiber reactivedyes which incorporate vinylsulfonyl and/or β-sulfatoethylsulfonylgroups. Such fiber reactive dyes are known from U.S. Pat. No. 5,810,890.

In certain embodiments, the polyamide yarns are dyed with fiber reactivedyes which incorporate halogen derivatives of nitrogen hetrocyclicgroups, such as, triazine, pyrimidine and quinoxaline. Such fiberreactive dyes are described, for example, in U.S. Pat. No. 6,869,453.

In other embodiments, the filaments comprise an amine component ofhexamethylene diamine.

In other embodiments, the filaments comprise an amine component which isa mixture of hexamethylene diamine with at least 20 wt % of methylpentamethylene diamine based on the total weight of diamine.

In still other embodiments, the polyamides may comprise nylon 6.

The following testing discussion can be used to characterize the variousparameters as discussed herein. Yarn tenacity and the yarn elongationcan be determined according to ASTM method D 2256-80 (known at the timeof filing the present disclosure with the United States Patent andTrademark Office) using an INSTRON tensile test apparatus (InstronCorp., Canton, Mass., USA 02021) and a constant cross head speed.Tenacity is expressed as centiNewtons per tex grams of force per denier,and the elongation percent is the increase in length of the specimen asa percentage of the original length at breaking load.

Yarn linear density evenness, also known as the yarn Uster percent (U%), can be determined using a Uster evenness tester 3, type C, which isknown in the art to the skilled person.

Polymer amine ends can be measured by directed titration withstandardized perchloric acid solution of weighed polymer samples takenup in solution after filteration to remove insoluble delusteringpigments.

The moisture regain of a polymer is measured by the following method. Asample (100 g) of the polymer is dried for 18 hours at 80° C. undervacuum. The initial moisture level of this dried polymer sample ispreferably measured using an Aquatrac (PET version (4 Digit); BrabenderMesstechnik) at 160° C. setting on about 1.9 g polymer. A moisture levelmeasured using this method of less than 0.5 w % is taken to indicatethat the polymer had been dried sufficiently.

The dried sample is then immersed in demineralised water (500 g) atambient temperature (20° C.) without any agitation. After 48 hours asample is removed (approx. 10 g) and patted dry with an absorbenttissue. A portion of the sample (approx. 5 g; weight of wet sample) isweighed accurately into a foil dish and placed in an oven at 80° C.under vacuum for 18 hours. The dish is removed and placed in adesiccator to cool, and then reweighed (weight left after drying). Thisprocedure is repeated at intervals thereafter (e.g. 72, 144, 190 and 220hours) up to 220 hours. Moisture uptake was determined by the followingcalculation:

${\frac{{{weight}\mspace{14mu} {of}\mspace{14mu} {wet}\mspace{14mu} {sample}} - {{weight}\mspace{14mu} {left}\mspace{14mu} {after}\mspace{14mu} {drying}}}{{weight}\mspace{14mu} {of}\mspace{14mu} {sample}\mspace{14mu} {after}\mspace{14mu} {drying}} \times 100} = {\% \mspace{14mu} {uptake}}$

The moisture regain of the polymer is defined as the moisture uptakeafter 220 hours or until the sample has reached moisture uptakeequilibrium (which is defined as a weight change of no more than 1% in a24 hour period), whichever is the earlier. Thus, if moisture uptakeequilibrium has not been reached by 220 hours the moisture regain is themoisture uptake at 220 hours. When the moisture uptake equilibrium isreached before 220 hours, the moisture regain is the average (mean) ofthe moisture uptake for the first two consecutive measurements taken atequilibrium.

The water wicking rates of fabrics constructed from the yarn can bemeasured by vertically immersing the bottom 1.8 inches (4.6 cm) of a oneinch (2.5 cm) wide strip of the scoured fabric in de-ionized water,visually determining the height of the water wicked up the fabric, andrecording the height as a function of time. “Initial wicking rate” meansthe average wicking rate during the first two minutes of the wickingtest.

A fabric or garment “Percent Dry Time” test can be used to characterizethe hydrophilic polyamide yarns, fabric and garments. Also known aspercent dry time tests or “horizontal wicking” determinations. Percentdry time tests are done using a balance and computer; e.g., Mettlerbalance AE163 and computer running a Mettler BalanceLink 3.0 program.The weight of a circular sample of fabric 2 inches (5.1 cm) in diameteris obtained and recorded. Using an automated pipette, 0.10 gram of tapwater is placed on the balance and its weight recorded. The circularfabric sample is immediately centered over and then placed on the water.The total weight of fabric and water is recorded at that time (time=zerominutes) and every two minutes thereafter for the next 30 minutes.Percent dry results for a given time are calculated according to thefollowing formula: % Dry=100=[W_(total)−W_(fabric))/W_(H2O)]×100.

EXAMPLES

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how toperform the methods and use the compositions and compounds disclosed andclaimed herein. Efforts have been made to ensure accuracy with respectto numbers (e.g., amounts, temperature, etc.), but some errors anddeviations should be accounted for. Unless indicated otherwise: partsare parts by weight, temperature is in ° C., and pressure is inatmospheres. Standard temperature and pressure are defined as 25° C. and1 atmosphere.

Example 1 Polyamide with 5 wt % Polyetheramine

Salt Prep

8380 g demineralized water was charged to flask and warmed to 35° C. 27g (0.185 mol) of adipic acid was charged and stirred to dissolve. 460 gof 80% Elastamine® RE2000 aqueous solution was charged, followed by 8077g of nylon 6,6 salt. The flask was left stirring until dissolved. Asample was taken and diluted, and the pH at 9.5% solids (approx.) waschecked and adjusted to the desired pH with HMD (or adipicacid)—initially pH 8.3 then lowered to 8.1 as feedback of results ofamine end groups (AEG) on polymer showed AEG was a bit too high. Solidswere checked using an IR heater moisture balance. The mixture was leftstirring overnight at 35° C.

Polymerization

The Salt Prep solution was added to a 24 L autoclave and 0.3 g of 48%aqueous Silwet L7605 antifoam (˜20 ppm on final polymer) was added.0.17% of Hombitan M titanium dioxide as a 40 wt % slurry was also addedduring serial heating Cycle 2 (C2). The polymer is targeted to have RV40; AEG 45; 0.17% TiO2 and containing 5 wt % Elastamine® RE2000.

For the polymerization, no evaporator was used, but rather a serialheating cycle 0 (C0) was developed to provide a position of saltconcentration similar to an evaporator batch—essentially in “C0,” themixture was heated up to around 185° C. and vented at 137 psia for aperiod of 87 minutes while the temperature was raised to 197° C. beforegoing into serial heating cycle (C1).

The process for the serial heating cycles was as follows: C1—T startedabout 197° C. finished 220° C., pressure reaching 265 psia defines endof C1, took about 18 mins; C2—265 psia held for 22 mins, T was raised to242° C.; serial heating cycle 3 (C3)—pressure let down to 14.5 psia(atm) over 35 mins, temperature was raised to final temperature of 275°C.; serial heating cycle 4 (C4)—6 mins at atm pressure while vacuumsystem being set up manually, applied vacuum of 400 mbar for 30 mins,then released with nitrogen back to atmospheric and held for 5 mins. Thepolymer was then cast. In certain cycle, polymer vacuum only held for 25mins as the polymerizing was slightly too much as evidenced by RV. Fourpolymers were manufactured and characterized with the results providedin Table 1.

TABLE 1 RV AEG YI Batch (target 40 (target 45 (yellowness Number +/−3)+/−3) L* a* b* Index) 1 42.22 48.25 80.65 −0.25 11.13 25.84 2 42.9246.55 79.78 0.56 14.63 31.25 3 39.65 45.82 80.56 0.18 12.43 28.1 4 39.4245.65 80.77 0.04 12.69 28.54A DSC trace of batch number 1 is provided in FIG. 1. A DSC trace ofbatch number 1 after reheat is provided in FIG. 2.

Example 2 Polyamide with 10 wt % of Polyetheramine

Salt Prep

8223 g demineralized water was charged to flask and warmed to 35° C., 54g (0.37 mol) of adipic acid was charged and stirred to dissolve, and 920g of 80% Elastamine® RE2000 aqueous solution was charged, followed by7627 g of nylon 6,6 salt. The flask was left stirring until dissolved. Asample was taken and diluted, and a pH at 9.5% solids (approx.) waschecked and adjusted to the pH between 8.3-8.1 with HMD (or adipicacid). Solids were checked using an IR heater moisture balance. Themixture was left stirring overnight at 35° C.

Polymerization

The Salt Prep solution was added to a 24 L autoclave. 2.51 g of sodiumhypophosphite monohydrate was added (to give 100 ppm P in finalpolymer), as was 0.3 g of 48% aqueous Silwet L7605 antifoam (˜20 ppm onfinal polymer). 0.17% of Hombitan M titanium dioxide as a 40 wt % slurrywas added during serial heating cycle 2 (C2). The polymer is targeted tohave RV 40; AEG 45; 0.17% TiO2 and containing 10 wt % Elastamine®RE2000.

For the polymerization, no evaporator was used, but rather a serialheating cycle 0 (C0) was developed to provide a position of saltconcentration similar to an evaporator batch—essentially in “C0” themixture was heated up to around 185° C. and vented at 137 psia for aperiod of 90 minutes while the temperature was raised to 197° C., beforegoing into serial heating cycle 1 (C1).

The process for the serial heating cycles was as follows: C1—T startedabout 202° C. finished 221° C., pressure reaching 265 psia defines endof C1; C2—265 psia held for 24 mins, T was raised to 244° C.; serialheating cycle 3 (C3)—pressure let down to 14.5 psia (atm) over 25 mins,temperature was raised to final temperature of 274° C.; and serialheating cycle 4 (C4)—11 mins at atm pressure while vacuum system beingset up manually, applied vacuum of 350 mbar for 24 mins, then releasedwith nitrogen back to atmospheric and held for 6 mins. The polymer wasthen cast. For batch numbers 6-10 in Table 2, the antifoam was 40 ppm.For batch numbers 6-9 in Table 2, the pressure was dropped at the end ofC2 to 218 psia before going into C3. The polymers manufactured werecharacterized with the results provided in Table 2.

TABLE 2 RV AEG YI Batch (target 40 (target 45 (yellowness Number +/−3)+/−3) L* a* b* Index) 5 36.62 44.39 75.41 2.56 21.59 41.5 6 42.0 45.275.43 3.38 22.12 42.8 7 41.1 44.6 77.46 2.78 22.05 41.78 8 42.2 46.676.70 3.41 21.97 42.65 9 41.1 45.5 75.62 3.22 22.11 42.85 10 43.2 46.074.92 2.89 23.52 45.46A DSC trace of batch number 5 is provided in FIG. 3. A DSC trace ofbatch number 5 after reheat is provided in FIG. 4. A DSC trace of batchnumber 6 is provided in FIG. 5.

Example 3 Polyamide with 15 wt % of Polyetheramine

Salt Prep

8362 g demineralized water was charged to flask and warmed to 35° C., 81g (0.555 mol) of adipic acid was charged and stirred to dissolve, and1380 g of 80% Elastamine® RE2000 aqueous solution was charged, followedby 7177 g of nylon 6,6 salt. The flask was left stirring untildissolved. A sample was taken and diluted, and a pH at 9.5% solids(approx.) was checked and adjusted to pH 8.1 with HMD. The solids werechecked using an IR heater moisture balance. The mixture was leftstirring overnight at 35° C.

Polymerization

The Salt Prep solution was added to a 24 L autoclave. 2.51 g of sodiumhypophosphite monohydrate was added (to give 100 ppm P in finalpolymer), as was 0.62 g of 48% aqueous Silwet L7605 antifoam (˜40 ppm onfinal polymer). 0.17% of Hombitan M titanium dioxide as a 40 wt % slurrywas added during serial heating cycle 2 (C2). The polymer is targeted tohave RV 40; AEG 45; 0.17% TiO2 and contains 15 wt % Elastamine® RE2000.

For polymerization, no evaporator was used. Rather, a serial heatingcycle 0 (C0) was developed to provide a position of salt concentrationsimilar to an evaporator batch—essentially in “C0” the mixture washeated up to around 185° C. and vented at 137 psia for a period of 87minutes while the temperature was raised to 197° C., before going intoserial heating cycle 1 (C1).

The process for the serial heating cycles was as follows: C1—T startedabout 197° C. finished 220° C., pressure reaching 265 psia defines endof C1, took about 17 mins; C2—265 psia held for 25 min, T was raised to243° C.; serial heating cycle 3 (C3)—pressure let down to 14.5 psia(atm) over 36 mins, temperature was raised to final temperature of 275°C.; and serial heating cycle 4 (C4)—5 mins at atm pressure while vacuumsystem being set up manually, applied vacuum of 350 mbar for 30 mins,then released with nitrogen back to atmospheric and held for 10 mins.The polymer was then cast. The polymer was characterized with theresults provided in Table 3.

TABLE 3 RV AEG YI Batch (target 40 (target 45 (yellowness Number +/−3)+/−3) L* a* b* Index) 11 30.32 53.82 75.13 4.21 25.5 47.23A DSC trace of batch number 11 is provided in FIG. 6. A DSC trace ofbatch number 11 after reheat is provided in FIG. 7.

Example 4 Moisture Regain

A sample (100 g) of each of the polymers obtained in examples 1 to 3 wasdried for 18 hours at 80° C. under vacuum. The initial moisture level ofthe dried polymer sample was measured using an Aquatrac (PET version (4Digit); Brabender Messtechnik) at 160° C. setting on about 1.9 gpolymer. A moisture level measured using this method of less than 0.5 w% was taken to indicate that the polymer had been dried sufficiently.

The dried sample was then immersed in demineralised water (500 g) atambient temperature (20° C.) without any agitation. After 48 hours asample was removed (approx. 10 g) and patted dry with an absorbenttissue. A portion of the sample (approx. 5 g; weight of wet sample) wasweighed accurately into a foil dish and placed in an oven at 80° C.under vacuum for 18 hours. The dish was removed and placed in adesiccator to cool, and then reweighed (weight left after drying). Thisprocedure was repeated at intervals thereafter (e.g. 72, 144, 190 and220 hours) up to 220 hours. Moisture uptake was determined by thefollowing calculation:

${\frac{{{weight}\mspace{14mu} {of}\mspace{14mu} {wet}\mspace{14mu} {sample}} - {{weight}\mspace{14mu} {left}\mspace{14mu} {after}\mspace{14mu} {drying}}}{{weight}\mspace{14mu} {of}\mspace{14mu} {sample}\mspace{14mu} {after}\mspace{14mu} {drying}} \times 100} = {\% \mspace{14mu} {uptake}}$

The results are summarized in Table 4.

TABLE 4 Moisture Moisture Moisture Moisture Moisture Uptake UptakeUptake Uptake Uptake (after (after (after (after (after Moisture Example48 hrs) 72 hrs) 144 hrs) 190 hrs) 220 hrs) Regain Control 2.19 2.5451.85 2.23 2.05 2.37 Example 1 7.06 9.06 11.30 12.76 12.95 12.86 Example2 10.6 13.39 16.99 18.20 17.90 18.05 Example 3 16.18 19.7 23.60 23.7024.25 23.65A plot showing the results summarized in Table 4 is provided in FIG. 8.

1. A polyamide, comprising a nylon and a polyetherdiamine, wherein thepolyetherdiamine is present in an amount ranging from about 1% to about20% by weight, the polyetherdiamine having a weight average molecularweight of at least 1500 and an Amine Hydrogen Equivalent Weight (AHEW)of less than 10 percent higher than the idealized AHEW for thepolyetherdiamine, wherein the AHEW is defined as the weight averagemolecular weight of the polyetherdiamine divided by the number of activehydrogen per molecule, and wherein the number of active amine hydrogenper molecule is determined using the procedure described in ISO
 9702. 2.A polyamide according to claim 1 having a moisture regain ranging fromabout 10% to about 30%.
 3. The polyamide of claim 1, wherein the nylonis nylon 6,6.
 4. The polyamide of claim 1, where in the nylon is nylon6.
 5. The polyamide of claim 1, wherein the polyamide has an elongationto break of from 20% to 90% when spun into a yarn
 6. The polyamide ofclaim 1, wherein the polyetherdiamine has an AHEW of less than 8 percenthigher than the idealized AHEW for the polyetherdiamine.
 7. Thepolyamide of claim 6, wherein the polyetherdiamine has an AHEW of lessthan 5 percent higher than the idealized AHEW for the polyetherdiamine.8. The polyamide of claim 6, wherein the polyetherdiamine has an AHEW ofless than 2 percent higher than the idealized AHEW for thepolyetherdiamine.
 9. The polyamide of claim 6, wherein thepolyetherdiamine has a weight average molecular weight of at least 2500.10. The polyamide of claim 9, wherein the polyetherdiamine has a weightaverage molecular weight of at least
 5000. 11. The polyamide of anypreceding claim, wherein the polyetherdiamine is present in an amountranging from about 1% to about 20% by weight.
 12. The polyamide of claim10, wherein the polyetherdiamine is present in an amount ranging fromabout 5 wt % to about 15 wt % by weight.
 13. The polyamide of claim 10,wherein the polyetherdiamine is present in an amount ranging from about10 wt % to about 15 wt % by weight.
 14. The polyamide of claim 10,wherein the polyetherdiamine is present in an amount ranging from about8 wt % to about 18 wt % by weight.
 15. The polyamide of claim 1, whereinthe polyamide has 25 to 130 amine end group gram-equivalents per 1000kilograms of polymer.
 16. The polyamide of claim 1, wherein thepolyamide has a relative viscosity ranging from about 25 to about 60,the relative viscosity calculated based on a formic acid test methodaccording to ASTM D789-86.
 17. The polyamide claim 1, wherein thepolyamide has a yellowness index from about 30 to about
 45. 18. Thepolyamide of claim 1, wherein the polyamide has an L* color coordinatefrom about 75 to about
 85. 19. The polyamide of claim 1, wherein thepolyamide has an a* color coordinate from about −5 to about
 5. 20. Thepolyamide of claim 1, wherein the polyamide has a b* color coordinatefrom about 5 to about
 25. 21. The polyamide of claim 1, furthercomprising 0.01 wt % to 1 wt % by weight of an optical brightener. 22.The polyamide of claim 1, further comprising 0.01 to 2 wt % by weight oftitanium dioxide.
 23. The polyamide of claim 1, further comprising 1 ppmto 500 ppm by weight of an anti-foaming additive.
 24. The polyamide ofclaim 1, further comprising a catalyst.
 25. The polyamide of claim 24comprising a phosphorus-containing catalyst.
 26. The polyamide of claim25, wherein the phosphorus-containing catalyst is present ranging from 5ppm to 1000 ppm phosphorus by weight in the polyamide.
 27. The polyamideof claim 25 wherein the catalyst is selected from the group consistingof phosphoric acid and salts thereof, phosphorous acid and saltsthereof, hypophosphoric acid arylphosphonic acids and salts thereof,arylphosphinic acids and salts thereof, sodium hypophosphite, manganesehypophosphite sodium phenylphosphinate, sodium phenylphosphonate,potassium phenylphosphinate, potassium phenylphosphonate,hexamethylenediammonium bis-phenylphosphinate, potassiumtolylphosphinate, and mixtures thereof.
 28. The polyamide of claim 27,wherein the catalyst is sodium hypophosphite.
 29. A compositioncomprising the polyamide as defined in claim
 1. 30. A process forproducing a polyamide, comprising: contacting a diacid, apolyetherdiamine, and any or all of nylon salt, aminoacid or lactam toform a mixture; and heating the mixture in a closed vessel to atemperature and autogenous pressure sufficient to polymerize the mixtureand form a polyamide.
 31. The process of claim 30, wherein the nylonsalt is a nylon 6,6 salt.
 32. The process of claim 30, wherein the nylonlactam is caprolactam.
 33. The process of claim 30, wherein contactingfurther comprises providing a catalyst to the mixture.
 34. The processof claim 33 wherein the catalyst contains phosphorus.
 35. The process ofclaim 34, wherein the phosphorus containing catalyst is present in anamount ranging from about from 5 ppm to about 1,000 ppm phosphorus byweight in the polyamide.
 36. The process of claim 34, wherein thecatalyst is selected from the group consisting of phosphoric acid,phosphorous acid, hypophosphoric acid, arylphosphonic acids,arylphosphinic acids, salts thereof, and mixtures thereof.
 37. Theprocess of claim 34, wherein the catalyst is selected from the groupconsisting of sodium hypophosphite, manganese hypophosphite sodiumphenylphosphinate, sodium phenylphosphonate, potassiumphenylphosphinate, potassium phenylphosphonate, hexamethylenediammoniumbis-phenylphosphinate, potassium tolylphosphinate, and mixtures thereof.38. The process of claim 37, wherein the catalyst is sodiumhypophosphite.
 39. The process of claim 30, wherein contacting furthercomprises providing an anti-foaming additive to the mixture, theantifoaming additive present in the polyamide in an amount ranging fromabout 1 ppm to about 500 ppm.
 40. The process of claim 30, whereincontacting further comprises providing an optical brightener to themixture, the optical brightener present in the polyamide in an amountranging from about 0.01 wt % to 1 wt %.
 41. The process of claim 30,wherein contacting further comprises providing titanium dioxide to themixture, the titanium dioxide present in the polyamide in an amountranging from about 0.01 wt % to 2 wt %.
 42. The process of claim 30,wherein the diacid is adipic acid, and the adipic acid is present in thepolyamide in an amount to give substantially equimolar proportions ofacid groups to amine groups of the polyetherdiamine.
 43. The process ofclaim 30, wherein the polyetherdiamine is present in the polyamide in anamount ranging from about 1 wt % to 20 wt %.
 44. The process of claim30, wherein the nylon is present in the polyamide in an amount rangingfrom about 50 wt % to 95 wt %.
 45. The process of claim 30, wherein thetemperature is from about 190° C. to about 320° C. and the autogenouspressure is from about 250 pounds per square inch absolute (psia) toabout 300 pounds per square inch absolute (psia).
 46. The process ofclaim 30, wherein heating is performed under vacuum at a pressure ofabout 200 mBar absolute.
 47. The process of claim 30, wherein heatingfurther comprises serial heating cycles, and wherein each heating cycleindividually comprises a heating temperature profile and a pressureprofile.
 48. The process of claim 47, wherein the serial heating cyclescomprise: a first heating cycle (C1) having a temperature startingbetween 170 to 215° C. and finishing between 190 to 230° C. over aperiod of 20 to 40 minutes under a pressure of between 130 to 300 psia;a second heating cycle (C2) having a temperature starting between 190 to230° C. and finishing at between 240 to 260° C. over a period of 20 to45 minutes under a pressure of between 130 to 300 psia; a third heatingcycle (C3) having a temperature starting between 240 and 260° C. andfinishing between 250 to 320° C. over a period of between 15 to 45minutes under a pressure of between 300 psia to atmospheric pressure;and a fourth heating cycle (C4) having a temperature starting between250 to 320° C. and finishing between 250 to 320° C. over a period of 15to 80 minutes under a pressure of between atmospheric pressure and about200 mBar absolute vacuum.
 49. The process of claim 30, wherein thepolyamide is characterised by a moisture regain of about 10 to about30%.
 50. A non-apparel textile yarn comprising the polyamide as definedin claim
 1. 51. A non-apparel textile comprising the non-apparel textileyarn of claim
 50. 52. The polyamide of claim 1, wherein thepolyetherdiamine has the following structure:


53. The polyamide of claim 1, wherein the polyetherdiamine is anα,ω-diamino poly(oxyalkylene-co-oxyalkylene ether) copolymer.
 54. Thepolyamide of claim 53, wherein the polyetherdiamine is made by reactingpolyethyleneglycol of molecular weight of about 2000 with three to fourmolecules of propyleneoxide.